Transport parameters of perovskite solar cells

30012015

This paper reports an excellent characterization of different tarnsport and recombination parameters of organolead trihalide MAPbX3 (MA = CH3NH3+; X = Br– or I–) single crystals. One important result is the very low density of traps that is infered from space charge limited current measurements

The fundamental properties and ultimate performance limits of organolead trihalide MAPbX3 (MA = CH3NH3+; X = Br– or I–) perovskites remain obscured by extensive disorder in polycrystalline MAPbX3 films. We report an antisolvent vapor-assisted crystallization approach that enables us to create sizable crack-free MAPbX3single crystals with volumes exceeding 100 cubic millimeters. These large single crystals enabled a detailed characterization of their optical and charge transport characteristics. We observed exceptionally low trap-state densities on the order of 109 to 1010 per cubic centimeter in MAPbX3 single crystals (comparable to the best photovoltaic-quality silicon) and charge carrier diffusion lengths exceeding 10 micrometers. These results were validated with density functional theory calculations.

Long, balanced electron and hole diffusion lengths greater than 100 nanometers in polycrystalline CH3NH3PbI3 are critical for highly efficient perovskite solar cells. We report that the diffusion lengths in CH3NH3PbI3 single crystals grown by a solution-growth method can exceed 175 μm under 1 sun illumination and exceed 3 mm under weak light for both electrons and holes. The internal quantum efficiencies approach 100% in 3 mm-thick single crystal perovskite solar cells under weak light. These long diffusion lengths result from greater carrier mobility, lifetime and dramatically smaller trap densities in the single crystals than polycrystalline thin-films. The long carrier diffusion lengths enabled the use of CH3NH3PbI3 in radiation sensing and energy-harvesting through gammavoltaic effect with an efficiency of 3.9% measured with an intense cesium-137 source.

State-of-the-art photovoltaics use high-purity, large-area, wafer-scale single-crystalline semiconductors grown by sophisticated, high-temperature crystal growth processes. We demonstrate a solution-based hot-casting technique to grow continuous, pinhole-free thin films of organometallic perovskites with millimeter-scale crystalline grains. We fabricated planar solar cells with efficiencies approaching 18%, with little cell-to-cell variability. The devices show hysteresis-free photovoltaic response, which had been a fundamental bottleneck for the stable operation of perovskite devices. Characterization and modeling attribute the improved performance to reduced bulk defects and improved charge carrier mobility in large-grain devices. We anticipate that this technique will lead the field toward synthesis of wafer-scale crystalline perovskites, necessary for the fabrication of high-efficiency solar cells, and will be applicable to several other material systems plagued by polydispersity, defects, and grain boundary recombination in solution-processed thin films.